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Vorpal is a sword Enchantment , added by RedPower 2, that increases the chances of mobs and players dropping a head on death. You can have up to 4 levels of this enchantment. Vorpal also gives a chance to deal greater damage, making it possible to kill mobs with one hit. This does not affect Wither Skeletons making this function purely for decorative purposes, and for making Creeper Fireworks.
The name Vorpal probably refers to the Lewis Carroll nonsense poem, the Jabberwocky, in which a beast (the Jabberwock) is beheaded with a Vorpal Sword.